Detergent compositions



3,009,882 DETERGENT COMPGSITEGNS Dav d Clarke, Bellevue, Wash and David B. Hester, Cmcmnati, Ohio, assignors to The Procter & Gamble Company, Qincinnati, Ghio, a corporation of Ohio No Drawing. Filed Feb. 12, 1959, Ser. No. 792,719

4 Claims. (Cl. 252- -116) In certain types of automatic laundering machines currently being marketed and which are structurally identified by a drum which is rotatable about an essentially horizontal axis and which carries internally projecting ribs mounted axially on its cylindrical wall, it has been found that general purpose laundering products characterized by the generation of a high volume of suds in use do not perform satisfactorily. In such drum-type machines which effect cleaning of clothes introduced into the drum by tumbling the clothes with a washing solution, general purpose laundering products including detergent compositions containing anionic synthetic sulfate and sulfonate detergents as the active synthetic detergent ingredient do not give their best cleaning performance because the suds formed at concentrations required for good cleansing tend to cushionthe movement of the clothes and diminish agitation to the point where inefficient cleaning results.

Recognition of this problem has resulted in the development of detergent compositions which are based upon nonionic synthetic detergents since such detergents possess cleansing ability with relatively low suds generation. Such nonionic detergent compositions are not, however, equal in washing performance to the heavy-duty anionic synthetic detergent compositions in the cleansing of heavily soiled cotton fabrics even though used in Wash ing concentrations above those customarily employed with general purpose heavy-duty laundering products.

As a consequence, a demand has arisen for detergent compositions which possess superior heavy-duty cleansing power but which are characterized by the generation of only a small amount of suds in use.

7 Efforts which have recently been made to cope with this specific sudsing and detergeney problem have resulted in the proposal of certain mixtures of nonionic compounds and saturated high molecular weight acyl-containing compounds in combination with anionic non-soap synthetics to depress sudsing of the anionic non-soap synthetic While maintaining an available high level of cleaning power. These recent advances have been made the subject of patent application Serial No. 587,505, filed May 28, 1956 (now US. Patent 2,954,348, granted September 27, 1960), and assigned by E. A. Schwoeppe to the assignee of the present application.

It has been found expedient in the industry, to market synthetic detergent compositions possessing heavy-duty cleaning power in laundering applications which have a high density, i.e. a high weight per unit volume. Such products are within the purview of the above referred to application of E. A. Schwoeppe.

It is an object of the present invention to provide improvements in such products.

it is a further object of this invention to provide heavyduty synthetic detergent compositions of the high denasz , Patented Novnfil, 1961 2 sity type which are essentially anionic, which have adequate heavy-duty cleansing power coupled with markedly depressed sudsing powder, and which also have improved caking characteristics.

Other objects will be readily apparent from the following detailed description.

Wherever herein the term high density is referred to in relation to a detergent composition it is to be understood that a detergent composition having a density in the range from about 0.55 to 0.65 gm./ cc. (about 5 ounces per cup) is contemplated. This is in contrast to the more prevalent type of granulated detergent composition in the market, and produced for the most part by spray drying techniques, which normally has a density in the range from about 0.28 to 0.35 gin/cc. (about 2.7 to 3.0 ounces per cup).

The present invention is based upon the observation that in the detergent compositions of the type disclosed in the aforementioned Schwoeppe application and which are also characterized by a high density, if a polypropoxy ether of n-butanol is substituted for the nonionic constituent of the compositions, an improvement in the caking characteristics of the composition is obtained. Moreover, this improved caking characteristic is obtained without substantial alteration oi the other desirable characteristics of such products, primary among which are the coupling of high cleansing ability with low sudsing power, i.e., generation of only a small volume of suds during use.

The particular constituent contemplated herein as a substitute for the nonionic detergent ingredient of the Schwoeppe composition is obtained by condensing about 45 mols of propylene oxide with 1 mol of butyl alcohol, the resulting propylene ether of butyl alcohol having a molecular Weight of about 2650, and having a viscosity of about 1905 in Saybolt Universal seconds at F. This product is commercially available under the trade name Ucon Fluid DA 1905 and as a matter of convenience will be referred to hereinafter by its trade name.

Such condensation product, although it has no specific hydrophobic and hydrophilic portions in the molecule as do the nonionicsynthetic detergent components of the Schwoeppe compositions, when substituted for the nonionic detergent component in such compositions, unexpectedly functions to synerglstically coact with the saturated high molecular weight acyl-containing component of those compositions to give the suds depressant effect of the nonionic detergent-high molecular weight acylcontaining component combination. In addition, the Ucon Fluid DA 1905 imparts to the compositions a greater resistance to caking under conditions of temperature and humidity which would normally promote caking in a particulate detergent product.

Thus, the detergent compositions of this invention are characterized by a high density and consist essentially of a.water-soluble alkali metal salt of a sulfuric reaction product having in its molecular structure an alkyl radical having from 8 to 18 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals, the said salt having pronounced sudsing and detergent power in aqueous solution, at least an equal weight of alkali metal polyphosphate, and as a suds depressant and caking inhibiting ingredient a mixture of (l) at least two compounds having acyl radicals of different carbon atom content and selected from the group consisting of saturated fatty acids having from about 14- to about 3lcarbon atoms and alkali metal soaps thereof, at least 50% of said compounds containing at least 16 carbon atoms, and (2) a water-insoluble compound comprising the reaction product of propylene oxide with butyl alcohol, the said reaction product having a molecular weight of about 2650 and a viscosity of about 1 905 Saybolt Universal seconds at 100 (Ucon Fluid DA 3 1905). This Ucon can be employed in the detergent composition in an amount from about 1% to about 10% by weight thereof, the amount in all cases, however, being suflicient to inhibit caking of the compositions.

The ability of the aforesaid Ucon to inhibit caking is' so pronounced that it has been possible to market the 7 high density products, to which this invention is directed, in plain paperboard cartons without concern that the product will cake in the carton if subjected to adverse humidity and temperature conditions. In contrast, if high density products of the type disclosed in the aforementioned application of E. A. Schwoeppe were to reach the consumer in the most desirable and acceptable physical condition, i.e., relatively completely uncaked, it was generally considered that packaging in asphalt impregnated cartons was necessary-the asphalt impregnation giving a degree of Water-impermeability to the carton so that the adverse effect which excessive humidity has upon product caking is minimized. This will be more evident from the following specific example in which all parts are by weight.

The ability of the products of the present invention to maintain a desirable free-flowing state even though packaged in untreated cartons results in a significant economic advantage, the cost of the untreated paperboard cartons being substantially less than that of asphalt-impregnated cartons.

Example] Two detergent products having the following high density compositions were prepared.

Parts by weight Product Product A B Alkyl benzene 'sulfonate whose alkyl radical was derived from polypropylene and averages about 12 carbon atoms Pluronic L-fi l-F-GS Mix 1 Fatty acid 2 Sodium tripolyphosphate. Sodium silicate (ratio of N 2 0- Sodium s fate Water md miscellaneous 1 Condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol andlhaving molecular weights of approximately 3,000 and 8,000 respec.- tive y.

2 A commercial mixture of fatty acids derived from hydrogenated fish oil, bearing the brand name Industrenc 250, having a constitution within the following range:

and a grade of 10 representing a product having the free flowing properties of dry sand. The actual grade given was an arbitrary valuerepresentative of the proportion of the total amount of product in the carton which would pour out under conti'olled and reproducible conditions Pour' grade Month Product A Product B It is evident from the above comparison that the prodhumid storage conditions such as are encountered in Florida. Such products were observed to retain their good caking characteristics for up to 6 months asevidenced by the following data. 7 Months: Pour grade It is to be appreciated that the proceeding specific example is not to be considered limiting of the presentinvention and that wide latitude in the choice and amounts of the various constituents of the compositions of this invention can 'be exercised without loss of the particular I benefits of the invention.

The anionic synthetic detergent to which, reference is made is generally referred to as a water-soluble salt of .an organic sulfuric reaction product having in its molec ular structure an alkyl radical having from about 8 to about 18 carbon atoms and a radical selected from the group consisting of sulfoni'c acid and sulfuric acid ester radicals. Import-ant examples of the synthetics which form an active part of the composition of the present invention are the sodium or potassium alkyl sulfates, es-

pecially those derived by sulfation of higher alcohols produced :by reduction of glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, es-

C pereent 0-2 C14" d0 816 010 do 3949 013 a ...(l.O 25-31 C do 7-14 0 and higher do 7 1-9 1 cr( O 505(g IV. maximum 1..

The preparations were carried outby first preparing a spray-dried granular composition containing substantially all of the ingredients of the respective compositions' ab ove except for the phosphate. 7 These spray-dried granular compositions were thenmechanically mixed with the sodiurn tripolyphosphate in the ratio of 1 part of phosphate to 3 parts of the. spray-dried granular composition by 7 weight. 7

The above products werepackaged in cartons which had received no special moistureproofing treatment, i.e.,

pecially those of the type described in U.S. LetterslPatent 2,220,099 and 2,477,383 in which the -alkyl groups contain from about 9 to about 15 carbon atoms; sodium alkyl glyceryl ether sulfonates,- especially] those ethers' having alkylgroups derived from tal-low and coconut oil; sodium coconut oil fatty acid monoglyceiidesulfatesj and sulfonates; sodium salts of sulfuric acidesters 'of the reaction product'of one mole of a higherfatty alcohol (eig. tallow or coconut oil alcohols) and about3 moles of ethylene oxide; and others known in the art, a number being specifically set' forth in the Byerly .U.S. Letters Patent 2,486,921 and Strain U.S. Lettersv Patent 2,486,922.

Such anionic synthetic detergents canbeutilized in ,the'

compositions 'of' the present invention in amounts from about 4 to about 40% by weight ofthecomposition. a

The high molecular weight acyl-containing component (fatty acid mixture orzsojaps thereof) which can be ern-' ployed in the practice of the present invention include mixturesof at least ,3 high molecular weight compounds 7 having acyl radicalsof'difierent carbon atom content, at

least.50%' of the said compounds .having at 1east-l6 carbonatoms. The presence of at least 5% of said Percent Myristic acid -25 Palmitic acid 0-50 Stearic acid 0-50 Arachidic acid 0-40 Behenic acid 0-40 Lignoceric id 0-25 Cerotic acid 0-25 Melissic acid 0-25 Oleie acid 0-30 Linoleic acid 0-10 Fatty acid compositions which find value in the practice of the present invention are commer-ical products known as Triple Pressed Stearic Acid, which is mainly a mixture of palrnitic and stearic acids, Hyfac 431, and Hydrofol 51 G6. Bulletins issued by the manufacturers report that the latter two products, which are particularly effective, are mixtures of fatty acids, derived from hydrogenated marine oils. Hyfac 431, for example, is reported to contain 8% myristic, 29% palmitic, 18% stearic, 26% arachidic, 17% behenic, and 2% oleic acids. Hydrofol 51 GG is reported to contain 7.5% C14 acid, C16 acid, C18 acid, C20 acid and 14.8% C acid. The unsaturated acid content of this mixture is said to be about 4.3%. Generally, any related fatty acid mixture having about -15% myristic acid, about 25-35% palmitic acid, about 15-30% arachidic acid, and about -20% behenic acid is of outstanding utility in the practice of the invention.

As above indicated, the mixture of alkali metal soaps of the fatty acids can be employed as well as the fatty acids or mixtures of fatty acids and soaps. Actually, the normal alkalinity desirable in the heavy-duty detergent-compositions contemplated herein is suflicient to convert at least a part of the fatty acid to soap, and in washing solutions of the present detergent compositions the fatty acids can exist in whole or in part as the alkali metal soaps.

The amount of acyl containing component can be varied depending upon the particular characteristics desired in the final composition and upon the amount of Ucon Fluid DA 1905 employed. Usuall the presence from about 1 to 10% of the fatty acid mixture or soap, calculated as fatty acid, and based upon the total product will suffice.

The amount of Ucon Fluid DA 1905 is variable depending upon the ultimate characteristics desired in the final product and also upon the amount of fatty acid mixture employed. Usually from about 1 to 10% of Ucon Fluid DA 1905 based upon the total product weight is sufficient. Alakaline detergent salts such as alkali metal pyrophosphate, tripolyphosphate or other higher polyphosphates, can be used in the compositions of the present invention in amounts from about 30 to 80% by weight of the composition.

In terms of the amount of anionic nonsoap detergent, the alkaline salts or builders may be present in equal or much greater amounts, for instance in amount as much as ten times that of the anionic detergent, or even more,

the upper limit of the salt to detergent ratio not being critical.

Many miscellaneous materials including moisture, coloring agents, fluorescent dyes, perfume, carboxymethyl cellulose, sodium carbonate and other alkaline salts as well as various other materials well known as constituents in detergent compositions can also be present.

Having thus described the invention, what is claimed 1. A detergent composition possessing heavy-duty cleansing power in laundering applications and characterized by a high density, depressed sudsing action, and resistance to caking which consists essentially of about 4% to about 40% of a water-soluble alkali metal salt of a sulfuric reaction product having in its molecular structure an alkyl radical having from 8 to 18 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals, the said salt having pronounced sudsing and detergent ability in aqueous solution, at least an equal weight of alkali metal polyphosphate, and, as a suds depressant and caking inhibitor, about 2% to about 20% of a mixture of (1) about 1% to about 10% of at least two compounds having acyl radicals of different carbon atom content and selected from the group consisting of saturated fatty acids having from about 14 to about 31 carbon atoms and water-soluble alkali metal soaps thereof, at least 50% of said compounds containing at least 16 carbon atoms, and (2) a water-insoluble compound comprising the reaction product of about 45 mole of propylene oxide with about 1 mol of butyl alcohol, the said reaction product having a molecular weight of about 2650 and a viscosity of about 1905 Saybolt Universal seconds at F. and being present in the detergent composition in an amount from about 1% to about 10% by weight thereof and sufficient to inhibit caking of the composition.

2. The detergent composition of claim 1 in which the acyl containing component corresponds to a mixture of about 0-2% lauric acid, about 816% myristic acid, about 39-49% palmitic acid, about 25-31% stearic acid, about 7-14% arachidic acid and about 1-9% behenic and higher fatty acids.

3. The detergent composition of claim 1 wherein the organic sulfuric reaction product is alkali metal alkyl benzene sulfonate in which the alkyl radical has an average of about 12 carbon atoms.

4. The detergent composition of claim 1 in which the alkali metal polyphosphate is sodium tripolyphosphate.

References Cited in the file of this patent UNITED STATES PATENTS 2,480,579 Holuba Aug. 30, 1949 2,560,839 Ayo et al July 17, 1951 2,874,123 Schaafsma et a1 Feb. 17, 1959 2,892,795 Dalton June 30, 1959 FOREIGN PATENTS 802,302 Great Britain Oct. 1, 1958 OTHER REFERENCES Ucon Fluids and Lubricants (1949), pub. of Carbide and Carbon Chem. Corp., pp. 10, 12 and 25.

Ucon Fluids and Lubricants (1956), pub. of Carbide and Car-bon Chem. Corp., p. 24. 

1. A DETERGENT COMPOSITION POSSESSING HEAVY-DUTY CLEANSING POWER IN LAUNDERING APPLICATION AND CHARACTERIZED BY A HIGH DENSITY, DEPRESSED SUDSING ACTION, AND RESISTANCE TO CAKING WHICH CONSISTS ESSENTIALLY OF ABOUT 4% TO ABOUT 40% OF A WATER-SOLUBLE ALKALI METAL SALT OF A SULFURIC REACTION-PRODUCT HAVING IN ITS MOLECULAR STRUCTURE AN ALKYL RADICAL HAVING FROM 8 TO 18 CARBON ATOMS AND A RADICAL SELECTED FROM THE GROUP CONSISTING OF SULFONIC ACID AND SULFURIC ACID ESTER RADICALS, THE SAID SALT HAVING PRONOUNCED SUDSING AND DETERGENT ABILITY IN AQUEOUS SOLUTION, AT LEAST AN EQUAL WEIGHT OF ALKALI METAL POLYPHOSPHATE, AND, AS A SUDS DEPRESSANT AND CAKING INHIBITOR, ABOUT 2% TO ABOUT 20% OF A MIXTURE OF (1) ABOUT 1% TO ABOUT 2% TO ABOUT LEAST TWO COMPOUNDS HAVING ACYL RADICALS OF DIFFERENT CARBON ATOM CONTENT AND SELECTED FROM THE GROUP CONSISTING OF SATURATED FATTY ACIDS HAVING FROM ABOUT 14 TO ABOUT 31 CARBON ATOMS AND WATER-SOLUBLE ALKALI METAL SOAPS THEREOF, AT LEAST 50% OF SAID COMPOUNDS CONTAINING AT LEAST 16 CARBON ATOMS, AND (2) A WATER-INSOLUBLE COMPOUND COMPRISING THE REACTION PRODUCT OF ABOUT 45 MOLS OF PROPYLENE OXIDE WITH ABOUT 1 MOL OF BUTYL ALCOHOL, THE SAID REACTION PRODUCT HAVING A MOLECULAR WEIGHT OF ABOUT 2650 AND A VISCOSITY OF ABOUT 1905 SAYBOLT UNIVERSAL SECONDS AT 100*F. AND BEING PERSENT IN THE DETERGENT COMPOSITION IN AN AMOUNT FROM ABOUT 1% TO ABOUT 10% BY WEIGHT THEREOF AND SUFFICIENT TO INHIBIT CAKING OF THE COMPOSITION. 